Method for producing an amine

ABSTRACT

Processes comprising: (i) providing a reactant selected from the group consisting of primary alcohols, secondary alcohols, aldehydes, ketones and mixtures thereof, and (ii) reacting the reactant with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary amines, secondary amines and mixtures thereof, in the presence of a catalyst comprising a zirconium dioxide- and nickel-containing catalytically active composition, to form an amine; wherein the catalytically active composition, prior to reduction with hydrogen, comprises oxygen compounds of zirconium, copper, and nickel, and one or more oxygen compounds of silver in an amount of 0.5 to 6% by weight, calculated as AgO.

The present invention relates to zirconium dioxide- andnickel-containing catalysts and to a process for preparing an amine byreacting a primary or secondary alcohol, aldehyde and/or ketone withhydrogen and a nitrogen compound selected from the group of ammonia,primary and secondary amines, in the presence of a zirconium dioxide-and nickel-containing catalyst.

The process products find use, inter alia, as intermediates in thepreparation of fuel additives (U.S. Pat. No. 3,275,554; DE-A-21 25 039and DE-A-36 11 230), surfactants, medicaments and crop protectants,hardeners for epoxy resins, catalysts for polyurethanes, intermediatesfor preparing quaternary ammonium compounds, plasticizers, corrosioninhibitors, synthetic resins, ion exchangers, textile assistants, dyes,vulcanization accelerants and/or emulsifiers.

U.S. Pat. No. 4,153,581 (Habermann) relates to the amination ofalcohols, aldehydes or ketones by means of specific Co/Cu catalystswhich comprise Fe, Zn and/or Zr.

U.S. Pat. No. 4,152,353 (Dow) relates to the amination of alcohols,aldehydes or ketones by means of specific Ni/Cu catalysts, whichcomprise Fe, Zn and/or Zr.

EP-A1-382 049 (BASF AG) discloses catalysts which compriseoxygen-containing zirconium, copper, cobalt and nickel compounds, andprocesses for the hydrogenating amination of alcohols. The preferredzirconium oxide content of these catalysts is from 70 to 80% by weight(loc. cit.: page 2, last paragraph; page 3, 3rd paragraph; examples).Although these catalysts feature good activity and selectivity, theyexhibit lifetimes in need of improvement.

EP-A2-514 692 (BASF AG) discloses catalysts comprising copper oxide,nickel oxide, and/or cobalt oxide, zirconium oxide and/or aluminum oxidefor the catalytic amination of alcohols in the gas phase with ammonia orprimary amines and hydrogen. This patent application teaches that theatomic ratio of nickel to copper in these catalysts must be from 0.1 to1.0, preferably from 0.2 to 0.5 (cf. loc. cit.: Example 1), sinceyield-reducing by-products otherwise occur to an increased degree in theamination of alcohols (loc. cit.: Examples 6 and 12). The support usedis preferably aluminum oxide (loc. cit.: Examples 1 to 5 and 7 to 11).

EP-A1-696 572 and EP-A-697 395 (both BASF AG) disclose catalystscomprising nickel oxide, copper oxide, zirconium oxide and molybdenumoxide for the catalytic amination of alcohols with nitrogen compoundsand hydrogen. Although these catalysts achieve high conversions, theycan form by-products which themselves or whose conversion products aretroublesome in the workup.

EP-A2-905 122 (BASF AG) describes a process for preparing amines fromalcohols and nitrogen compounds using a catalyst whose catalyticallyactive composition comprises oxygen compounds of zirconium, copper andnickel, and no oxygen compounds of cobalt or molybdenum.

EP-A-1 035 106 (BASF AG) relates to the use of catalysts comprisingoxygen compounds of zirconium, copper and nickel for preparing amines byaminating hydrogenation of aldehydes or ketones.

EP-A1-963 975 and EP-A2-1 106 600 (both BASF AG) describe processes forpreparing amines from, respectively, alcohols and aldehydes or ketones,and nitrogen compounds using a catalyst whose catalytically activecomposition comprises 22-40% by weight (or 22-45% by weight) of oxygencompounds of zirconium, 1-30% by weight of oxygen compounds of copperand in each case 15-50% by weight (or 5-50% by weight) of oxygencompounds of nickel and cobalt.

WO-A-03/076386 and EP-A1-1 431 271 (both BASF AG) also teach catalystsof the abovementioned type for aminations.

WO-A1-03/051508 (Huntsman Petrochemical Corp.) relates to processes foraminating alcohols using specific Cu/Ni/Zr/Sn catalysts which, in afurther embodiment, comprise Cr in place of Zr (see page 4, lines10-16).

European patent application No. 06101339.7 of Feb. 6, 2006 (BASF AG)describes a process for preparing aminodiglycol (ADG) and morpholine byreacting diethylene glycol (DEG) with ammonia in the presence of aheterogeneous transition metal catalyst, the catalytically activecomposition of the catalyst, before the treatment with hydrogen,comprising oxygen compounds of aluminum and/or zirconium, copper, nickeland cobalt, and the shaped catalyst body having specific dimensions.

Four parallel European patent applications with the same filing date(all BASF AG) relate to particular doped zirconium dioxide-, copper- andnickel-containing catalysts and to their use in processes for preparingan amine by reacting a primary or secondary alcohol, aldehyde and/orketone with hydrogen and ammonia, a primary or secondary amine.

When the very active catalysts of the prior art are used, including inparticular the catalysts according to EP-A1-696 572, EP-A1-963 975 andEP-A2-1 106 600 (see above), there may be an increased tendency todecarbonylation of the carbonyl function (which may have formed as anintermediate) at elevated temperature in the reactants (alcohols,aldehyde, ketone). The formation of methane by hydrogenation of carbonmonoxide (CO) leads, owing to the large amount of heat of hydrogenationreleased, to a “runaway risk”, i.e. an uncontrolled temperature rise inthe reactor. When CO is scavenged by amines, methyl-containing secondarycomponents are formed.

In the amination of diethylene glycol (DEG), there is, for example, anincreased tendency to form undesired methoxyethanol ormethoxyethylamine.

In the case of the example of the amination of diethylene glycol (DEG),the “decarbonylation” is viewed in particular as the sum of undesiredcomponents (methanol, methoxyethanol, methoxyethylamine,N-methylmorpholine and methoxy-ethylmorpholine) which are formed fromDEG via methoxyethanol according to the reaction network:

The reaction mechanism of the amination of primary or secondary alcoholsis assumed to be that the alcohol is initially dehydrogenated to thecorresponding aldehyde at a metal site. In this reaction, the copper issuspected to be of particular significance as a dehydrogenationcomponent. When aldehydes are used for the amination, this step is notneeded.

The aldehyde formed or used can be aminated by reaction with ammonia orprimary or secondary amine with elimination of water and subsequenthydrogenation. This condensation of the aldehyde with the abovementionednitrogen compound is suspected to be catalyzed by acidic sites of thecatalyst. In an undesired side reaction, the aldehyde can also bedecarbonylated, i.e. in that the aldehyde function is eliminated as CO.The decarbonylation or methanization is suspected to take place at ametallic site. The CO is hydrogenated to methane over the hydrogenationcatalyst, so that the methane formation indicates the extent ofdecarbonylation. The decarbonylation forms the abovementioned undesiredby-products, for example methoxyethanol and/or methoxyethylamine in theabovementioned case.

The desired condensation of the aldehyde with ammonia or primary orsecondary amine and the undesired decarbonylation of the aldehyde areparallel reactions, of which the desired condensation is suspected to beacid-catalyzed, while the undesired decarbonylation is catalyzed bymetallic sites.

It was an object of the present invention to improve the economicviability of existing processes for hydrogenating amination of aldehydesor ketones and the amination of alcohols, and to remedy one or moredisadvantages of the prior art, especially the abovementioneddisadvantages. The intention was to find catalysts which can be preparedindustrially in a simple manner and which enable the above-mentionedaminations to be performed with high conversion, high yield, space-timeyields (STY), selectivity, catalyst lifetime with simultaneously highmechanical stability of the shaped catalyst body and low “runaway risk”.The catalysts should accordingly have a high activity and have highchemical and mechanical stability under the reaction conditions.

[Space-time yields are reported in “amount of product/(catalystvolume·time)” (kg/(I_(cat.)·h)) and/or “amount of product/(reactorvolume·time)” (kg/(I_(reactor)·h)].

Accordingly, we have found a process for preparing an amine by reactinga primary or secondary alcohol, aldehyde and/or ketone with hydrogen anda nitrogen compound selected from the group of ammonia, primary andsecondary amines, in the presence of a zirconium dioxide- andnickel-containing catalyst, wherein the catalytically active compositionof the catalyst, before its reduction with hydrogen, comprises oxygencompounds of zirconium, copper and nickel, and in the range from 0.5 to6% by weight of oxygen compounds of silver, calculated as AgO.

We have also found catalysts which comprise oxygen compounds ofzirconium, copper and nickel, and in the range from 0.5 to 6% by weightof oxygen compounds of silver, calculated as AgO.

More particularly, we have found catalysts whose catalytically activecomposition, before their reduction with hydrogen, comprises in therange from

10 to 75% by weight of oxygen compounds of zirconium, calculated asZrO₂,1 to 30% by weight of oxygen compounds of copper, calculated as CuO,10 to 70% by weight of oxygen compounds of nickel, calculated as NiO,and0.5 to 6% by weight of oxygen compounds of silver, calculated as AgO,and their use in the abovementioned amination process, especially in theprocess for reacting DEG with ammonia.

In accordance with the invention, it has been recognized that theactivity of the catalyst for the amination of primary or secondaryalcohols, aldehydes and/or ketones in the presence of H₂, for examplethe amination of diethylene glycol (DEG) with ammonia to giveaminodiglycol and morpholine, as a result of the additional content inthe zirconium-copper-nickel catalysts of Ag, essentially at leastremains constant, but the extent of the undesired decarbonylationreaction simultaneously decreases and hence the selectivity of theamination reaction increases.

The process can be performed continuously or batchwise. Preference isgiven to a continuous method.

For the synthesis in the gas phase, the reactants are fed to the reactorin a controlled manner, preferably in a cycle gas stream, evaporated andin gaseous form. Suitable amines for a gas phase synthesis are amineswhich, owing to their boiling points and the boiling points of theirreactants, can be kept in the gas phase within the process parameters byprocess technology means. The cycle gas serves firstly to evaporate thereactants and secondly as a reactant for the amination.

In the cycle gas method, the starting materials (alcohol, aldehydeand/or ketone, hydrogen and the nitrogen compound) are evaporated in acycle gas stream and fed to the reactor in gaseous form.

The reactants (alcohol, aldehyde and/or ketone, the nitrogen compound)may also be evaporated as aqueous solutions and passed to the catalystbed with the cycle gas stream.

Preferred reactors are tubular reactors. Examples of suitable reactorswith cycle gas stream can be found in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Ed., Vol. B 4, pages 199-238, “Fixed-BedReactors”.

Alternatively, the reaction is advantageously effected in a tube bundlereactor or in a single-stream plant.

In a single-stream plant, the tubular reactor in which the reactionproceeds can consist of a series connection of a plurality of (e.g. twoor three) individual tubular reactors. Optionally, an intermediateintroduction of feed (comprising the reactant and/or ammonia and/or H₂)and/or cycle gas and/or reactor effluent from a downstream reactor ispossible here in an advantageous manner.

The cycle gas flow rate is preferably in the range from 40 to 1500 m³(at operating pressure)/[m³ of catalyst (bed volume)·h], in particularin the range from 100 to 700 m³ (at operating pressure)/[m³ of catalyst(bed volume)·h].

The cycle gas comprises preferably at least 10% by volume, particularlyfrom 50 to 100% by volume, very particularly from 80 to 100% by volumeof H₂.

For the synthesis in the liquid phase, suitable reactants and productsare all of those which have high boiling points or are thermally labile.In these cases, a further advantage is that it is possible to dispensewith evaporation and recondensation of the amine in the process.

In the process according to the invention, the catalysts are preferablyused in the form of catalysts which consist only of catalytically activecomposition and, if appropriate, a shaping assistant (for examplegraphite or stearic acid) if the catalyst is used as a shaped body, i.e.do not comprise any further catalytically active ingredients.

In this connection, the oxidic support material zirconium dioxide (ZrO₂)is considered to be included in the catalytically active composition.

The catalysts are used in such a way that the catalytically activecomposition ground to powder is introduced into the reaction vessel orthat the catalytically active composition, after grinding, mixing withshaping assistants, shaping and heat treatment, is arranged in thereactor as shaped catalyst bodies—for example as tablets, spheres,rings, extrudates (e.g. strands).

The concentration data (in % by weight) of the components of thecatalyst are based in each case, unless stated otherwise, on thecatalytically active composition of the finished catalyst after its lastheat treatment and before its reduction with hydrogen.

The catalytically active composition of the catalyst, after its lastheat treatment and before its reduction with hydrogen, is defined as thesum of the masses of the catalytically active constituents and of theabovementioned catalyst support materials, and comprises essentially thefollowing constituents:

zirconium dioxide (ZrO₂), oxygen compounds of copper and nickel andoxygen compounds of silver.

The sum of the abovementioned constituents of the catalytically activecomposition is typically from 70 to 100% by weight, preferably from 80to 100% by weight, more preferably from 90 to 100% by weight,particularly >95% by weight, very particularly >98% by weight, inparticular >99% by weight, for example more preferably 100% by weight.

The catalytically active composition of the inventive catalysts andthose used in the process according to the invention may also compriseone or more elements (oxidation stage 0) or their inorganic or organiccompounds selected from groups I A to VI A and I B to VII B and VIII ofthe Periodic Table of the Elements.

Examples of such elements and their compounds are:

transition metals such as Re or rhenium oxides, Mn or MnO₂, W ortungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobiumoxalate, V or vanadium oxides or vanadyl pyrophosphate; lanthanides suchas Ce or CeO₂, or Pr or Pr₂O₃; alkali metal oxides such as Na₂O; alkalimetal carbonates such as Na₂CO₃; alkaline earth metal oxides such asSrO; alkaline earth metal carbonates such as MgCO₃, CaCO₃ and BaCO₃;boron oxide (B₂O₃).

The catalytically active composition of the inventive catalysts andthose used in the process according to the invention preferably does notcomprise any cobalt, more preferably does not comprise any cobalt, anyruthenium, any iron and/or any zinc.

The catalytically active composition of the catalyst, before itsreduction with hydrogen comprises, preferably in the range from 1.0 to4% by weight, particularly in the range from 1.2 to 3.5% by weight, moreparticularly in the range from 1.3 to 3% by weight, very particularly inthe range from 1.4 to 2.5% by weight, of oxygen compounds of silver,calculated as AgO.

In addition, the catalytically active composition of the catalyst,before its reduction with hydrogen, comprises preferably in the rangefrom

10 to 75% by weight, particularly from 25 to 65% by weight, moreparticularly from 30 to 55% by weight, of oxygen compounds of zirconium,calculated as ZrO₂,1 to 30% by weight, particularly from 2 to 25% by weight, moreparticularly from 5 to 15%, by weight of oxygen compounds of copper,calculated as CuO, and10 to 70% by weight, particularly from 20 to 60% by weight, moreparticularly from 30 to 50% by weight, of oxygen compounds of nickel,calculated as NiO.

The molar ratio of nickel to copper is preferably greater than 1, morepreferably greater than 1.2, even more preferably in the range from 1.8to 8.5.

To prepare the catalysts used in the process according to the invention,various processes are possible. They are, for example, obtainable bypeptizing pulverulent mixtures of the hydroxides, carbonates, oxidesand/or other salts of the components with water and subsequentlyextruding and heat-treating the composition thus obtained.

Preference is given to preparing the inventive catalysts by employingprecipitation methods. For example, they can be obtained bycoprecipitating the nickel, copper and doping metal components from anaqueous salt solution comprising these elements by means of bases in thepresence of a slurry of a sparingly soluble, oxygen-containing zirconiumcompound and subsequently washing, drying and calcining the resultingprecipitate. The sparingly soluble oxygen-containing zirconium compoundsused may, for example, be zirconium dioxide, zirconium oxide hydrate,zirconium phosphates, zirconium borates and zirconium silicates. Theslurries of the sparingly soluble zirconium compounds can be prepared bysuspending fine powders of these compounds in water with vigorousstirring. Advantageously, these slurries are obtained by precipitatingthe sparingly soluble zirconium compounds from aqueous zirconium saltsolutions by means of bases.

The inventive catalysts are preferably prepared by means of acoprecipitation (mixed precipitation) of all of their components. Tothis end, an aqueous salt solution comprising the catalyst components isappropriately admixed with an aqueous base—for example sodium carbonate,sodium hydroxide, potassium carbonate or potassium hydroxide—under hotconditions with stirring until the precipitation is complete. It is alsopossible to work with alkali metal-free bases such as ammonia, ammoniumcarbonate, ammonium hydrogencarbonate, ammonium carbamate, ammoniumoxalate, ammonium malonate, urotropin, urea, etc. The type of salts usedis generally not critical: since the principal factor in this procedureis the water solubility of the salts, a criterion is their good watersolubility required to prepare these comparatively highly concentratedsalt solutions. It is considered to be self-evident that, when selectingthe salts of the individual components, the salts selected will ofcourse only be those with anions which do not lead to disruption,whether by causing undesired precipitations or by complicating orpreventing the precipitation by complex formation.

The precipitates obtained in these precipitation reactions are generallychemically inhomogeneous and consist, inter alia, of mixtures of theoxides, oxide hydrates, hydroxides, carbonates and insoluble and basicsalts of the metals used. It may be found to be favorable for thefilterability of the precipitates when they are aged, i.e. when they areleft for a certain time after the precipitation, if appropriate underhot conditions or while passing air through.

The precipitates obtained by these precipitation processes are processedfurther as usual to give the inventive catalysts. First, theprecipitates are washed. The content of alkali metal which has beensupplied by the (mineral) base which may have been used as a precipitantcan be influenced via the duration of the washing operation and via thetemperature and amount of the washing water. In general, prolonging thewashing time or increasing the temperature of the washing water willdecrease the content of alkali metal. After the washing, theprecipitated material is generally dried at from 80 to 200° C.,preferably at from 100 to 150° C., and then calcined. The calcination isperformed generally at temperatures between 300 and 800° C., preferablyat from 400 to 600° C., in particular at from 450 to 550° C.

The inventive catalysts may also be prepared by impregnating zirconiumdioxide (ZrO₂) which is present, for example, in the form of powder orshaped bodies such as extrudates, tablets, spheres or rings.

The zirconium dioxide is used, for example, in the monoclinic ortetragonal form, preferably in the monoclinic form.

Shaped bodies can be produced by the customary processes.

The impregnation is likewise effected by the customary processes, asdescribed, for example, in A. B. Stiles, Catalyst Manufacture-Laboratoryand Commercial Preparations, Marcel Dekker, New York (1983), by applyingan appropriate metal salt solution in each case in one or moreimpregnation stages, the metal salts used being, for example,appropriate nitrates, acetates or chlorides. After the impregnation, thecomposition is dried and optionally calcined.

The impregnation can be effected by the so-called incipient wetnessmethod, in which the zirconium dioxide is moistened, in accordance withits water uptake capacity, up to a maximum of saturation with theimpregnation solution. The impregnation can also be effected insupernatant solution.

In the case of multistage impregnation processes, it is appropriate todry and optionally to calcine between individual impregnation steps.Multistage impregnation can be employed particularly advantageously whenthe zirconium dioxide is to be loaded with a relatively large amount ofmetal.

To apply the metal components to the zirconium dioxide, the impregnationcan be effected simultaneously with all metal salts or successively inany sequence of the individual metal salts.

Subsequently, the catalysts prepared by impregnation are dried andpreferably also calcined, for example within the calcination temperatureranges already specified above.

After the calcination, the catalyst is appropriately conditioned,whether it be by grinding to a certain particle size or by mixing it,after it has been ground, with shaping assistants such as graphite orstearic acid, compressing it by means of a press to moldings, forexample tablets, and heat-treating. The heat treatment temperaturescorrespond preferably to the temperatures in the calcining.

The catalysts prepared in this way comprise the catalytically activemetals in the form of a mixture of their oxygen compounds, i.e. inparticular in the form of oxides and mixed oxides.

The catalysts prepared, for example, as described above are stored assuch and, if appropriate, treated. Before they are used as catalysts,they are typically prereduced. However, they can also be used withoutprereduction, in which case they are reduced under the conditions of thehydrogenating amination by the hydrogen present in the reactor.

For prereduction, the catalysts are exposed to a nitrogen-hydrogenatmosphere first at preferably from 150 to 200° C. over a period of, forexample, from 12 to 20 hours, and then treated in a hydrogen atmosphereat preferably from 200 to 400° C. for another up to approx. 24 hours.This prereduction reduces a portion of the oxygen-containing metalcompounds present in the catalysts to the corresponding metals, so thatthey are present together with the different types of oxygen compoundsin the active form of the catalyst.

A further advantage of the inventive catalysts is their mechanicalstability, i.e. their hardness. The mechanical stability can bedetermined by the measurement of the so-called side crushing strength.For this purpose, the shaped catalyst body, for example the catalysttablet, is stressed with increasing force between two parallel platesuntil fracture of the shaped catalyst body occurs, and this stress mayact, for example, on the cylindrical surface of catalyst tablets. Theforce registered when the shaped catalyst body fractures is the sidecrushing strength.

The process according to the invention is preferably performedcontinuously, the catalyst preferably being arranged in the reactor as afixed bed. It is possible for the flow toward the fixed catalyst bed tobe either from the top or from the bottom. The gas stream is adjusted interms of temperature, pressure and flow rate in such a way that evenrelatively high-boiling reaction products remain in the gas phase.

The aminating agent may, with regard to the alcoholic hydroxyl group oraldehyde group or keto group to be aminated, be used in stoichiometric,sub- or superstoichiometric amounts.

In the case of the amination of alcohols, aldehydes or ketones withprimary or secondary amines, the amine is preferably used in anapproximately stoichiometric amount or slightly superstoichiometricamount per mole of alcoholic hydroxyl group, aldehyde group or ketogroup to be aminated.

The amine component (nitrogen compound) is used preferably in from 0.90to 100 times the molar amount, especially in from 1.0 to 10 times themolar amount, based in each case on the alcohol, aldehyde and/or ketoneused.

Especially ammonia is used generally with a from 1.5- to 250-fold,preferably from 2- to 100-fold, especially from 2- to 10-fold molarexcess per mole of alcoholic hydroxyl group, aldehyde group or ketogroup to be converted.

Higher excesses both of ammonia and of primary or secondary amines arepossible.

Preference is given to employing an offgas flow rate of from 5 to 800standard cubic meters/h, especially from 20 to 300 standard cubicmeters/h.

The amination of the primary or secondary alcohol groups, aldehydegroups or keto groups of the reactant can be performed in the liquidphase or in the gas phase. Preference is given to the fixed bed processin the gas phase.

When working in the liquid phase, the reactants (alcohol, aldehyde orketone plus ammonia or amine) are passed simultaneously, includinghydrogen, over the catalyst, which is typically disposed in a fixed bedreactor preferably heated externally, in the liquid phase at pressuresof generally from 5 to 30 MPa (50-300 bar), preferably from 5 to 25 MPa,more preferably from 15 to 25 MPa, and temperatures of generally from 80to 350° C., particularly from 100 to 300° C., preferably from 120 to270° C., more preferably from 130 to 250° C., in particular from 170 to230° C. Both a trickle mode and a liquid-phase mode are possible. Thecatalyst hourly space velocity is generally in the range from 0.05 to 5kg, preferably from 0.1 to 2 kg and more preferably from 0.2 to 0.6 kgof alcohol, aldehyde or ketone per liter of catalyst (bed volume) andhour. If appropriate, the reactants can be diluted with a suitablesolvent such as tetrahydrofuran, dioxane, N-methylpyrrolidone orethylene glycol dimethyl ether. It is appropriate to heat the reactantsbefore they are fed into the reaction vessel, preferably to the reactiontemperature.

When working in the gas phase, the gaseous reactants (alcohol, aldehydeor ketone plus ammonia or amine) are passed over the catalyst in thepresence of hydrogen in a gas stream, preferably hydrogen, selected soas to be sufficiently large for evaporation, at pressures of generallyfrom 0.1 to 40 MPa (from 1 to 400 bar), preferably from 0.1 to 10 MPa,more preferably from 0.1 to 5 MPa. The temperatures for the amination ofalcohols are generally from 80 to 350° C., particularly from 100 to 300°C., preferably from 120 to 270° C., more preferably from 160 to 250° C.The reaction temperatures in the hydrogenating amination of aldehydesand ketones are generally from 80 to 350° C., particularly from 90 to300° C., preferably from 100 to 250° C. The flow to the fixed catalystbed may be either from above or from below. The required gas stream ispreferably obtained by a cycle gas method.

The catalyst hourly space velocity is generally in the range from 0.01to 2 and preferably from 0.05 to 0.5 kg of alcohol, aldehyde or ketoneper liter of catalyst (bed volume) and hour.

The hydrogen is fed to the reaction generally in an amount of from 5 to400 l, preferably in an amount of from 50 to 200 l per mole of alcohol,aldehyde or ketone component, the amounts in liters each having beenconverted to standard conditions (S. T. P.). The performance of theamination of aldehydes or ketones differs from that of the amination ofalcohols in that at least stoichiometric amounts of hydrogen need to bepresent in the amination of aldehydes and ketones.

Both in the case of operation in the liquid phase and in the case ofoperation in the gas phase, it is possible to use higher temperaturesand higher overall pressures and catalyst hourly space velocities. Thepressure in the reaction vessel, which results from the sum of thepartial pressures of the aminating agent, of the alcohol, aldehyde orketone, and of the reaction products formed and, if appropriate, of thesolvent used at the temperatures specified, is appropriately increasedby injecting hydrogen up to the desired reaction pressure.

Both in the case of continuous operation in the liquid phase and in thecase of continuous operation in the gas phase, the excess aminatingagent can be circulated together with the hydrogen.

When the catalyst is arranged as a fixed bed, it may be advantageous forthe selectivity of the reaction to mix the shaped catalyst bodies in thereactor with inert packings, to “dilute” them as it were. The proportionof packings in such catalyst preparations may be from 20 to 80 parts byvolume, particularly from 30 to 60 parts by volume and in particularfrom 40 to 50 parts by volume.

The water of reaction formed in the course of the reaction (in each caseone mole per mole of alcohol group, aldehyde group or keto groupconverted) generally does not have a disruptive effect on the degree ofconversion, the reaction rate, the selectivity and the catalystlifetime, and is therefore appropriately not removed therefrom until theworkup of the reaction product, for example by distillation.

After the reaction effluent has appropriately been decompressed, theexcess hydrogen and any excess aminating agent present are removedtherefrom and the resulting crude reaction product is purified, forexample by a fractional rectification. Suitable workup processes aredescribed, for example, in EP-A-1 312 600 and EP-A-1 312 599 (both BASFAG). The excess aminating agent and the hydrogen are advantageouslyreturned back into the reaction zone. The same applies to anyincompletely converted alcohol, aldehyde or ketone component.

Unconverted reactants and any suitable by-products which are obtainedcan be returned back into the synthesis. Unconverted reactants can beflowed again in the cycle gas stream over the catalyst bed in batchwiseor continuous mode after condensation of the products in the separator.

Aminating agents in the process according to the invention are, as wellas ammonia, primary and secondary amines.

It is possible by the process according to the invention to prepare, forexample, amines of the formula I

in which

-   -   R¹, R² are each hydrogen (H), alkyl such as C₁₋₂₀-alkyl,        cycloalkyl such as C₃₋₁₂-cycloalkyl, alkoxyalkyl such as        C₂₋₃₀-alkoxyalkyl, dialkylaminoalkyl such as        C₃₋₃₀-dialkylaminoalkyl, aryl, aralkyl such as C₇₋₂₀-aralkyl and        alkylaryl such as C₇₋₂₀-alkylaryl, or together are        —(CH₂)_(j)—X—(CH₂)_(k)—,    -   R³, R⁴ are each hydrogen (H), alkyl such as C₁₋₂₀-alkyl,        cycloalkyl such as C₃₋₁₂-cycloalkyl, hydroxyalkyl such as        C₁₋₂₀-hydroxyalkyl, aminoalkyl such as C₁₋₂₀-aminoalkyl,        hydroxyalkylaminoalkyl such as C₂₋₂₀-hydroxyalkylaminoalkyl,        alkoxyalkyl such as C₂₋₃₀-alkoxyalkyl, dialkylaminoalkyl such as        C₃₋₃₀-dialkylamino-alkyl, alkylaminoalkyl such as        C₂₋₃₀-alkylaminoalkyl, R⁵—(OCR⁶R⁷CR⁸R⁹)_(n)—(OCR⁶R⁷), aryl,        heteroaryl, aralkyl such as C₇₋₂₀-aralkyl, heteroarylalkyl such        as C₄₋₂₀-heteroarylalkyl, alkylaryl such as C₇₋₂₀-alkylaryl,        alkylheteroaryl such as C₄₋₂₀-alkylheteroaryl, and        Y—(CH₂)_(m)—NR⁵—(CH₂)_(q) or, together, —(CH₂)_(l)—X—(CH₂)_(m)—        or    -   R² and R⁴ together are —(CH₂)_(l)—X—(CH₂)_(m)—,    -   R⁵, R¹⁰ are each hydrogen (H), alkyl such as C₁₋₄-alkyl,        alkylphenyl such as C₇₋₄₀-alkylphenyl,    -   R⁶, R⁷, R⁸, R⁹ are each hydrogen (H), methyl or ethyl,    -   X is CH₂, CHR⁵, oxygen (O), sulfur (S) or NR⁵,    -   Y is N(R¹⁰)₂, hydroxyl, C₂₋₂₀-alkylaminoalkyl or        C₃₋₂₀-dialkylaminoalkyl,    -   n is an integer from 1 to 30 and    -   j, k, l, m, q are each integers from 1 to 4.

The process according to the invention therefore preferably finds usefor preparing an amine I by reacting a primary or secondary alcohol ofthe formula II

and/or an aldehyde and/or a ketone of the formula VI or VII

with a nitrogen compound of the formula III

where R¹, R², R³ and R⁴ are each as defined above.

The reactant alcohol may also be an amino alcohol, for example an aminoalcohol of the formula II.

As is evident from the definitions of the R² and R⁴ radicals, thereaction can also be effected intramolecularly in an appropriate aminoalcohol, amino ketone or amino aldehyde.

To prepare the amine I, in a purely formal sense, a hydrogen atom of thenitrogen compound III is accordingly replaced by the R⁴(R³)CH— radicalwith release of one molar equivalent of water.

The process according to the invention preferably also finds use in thepreparation of a cyclic amine of the formula IV

in which

-   R¹¹ and R¹² are each hydrogen (H), alkyl such as C₁- to C₂₀-alkyl,    cycloalkyl such as C₃- to C₁₂-cycloalkyl, aryl, heteroaryl, aralkyl    such as C₇- to C₂₀-aralkyl, and alkylaryl such as C₇- to    C₂₀-alkylaryl,-   Z is CH₂, CHR⁵, oxygen (O), NR⁵ or NCH₂CH₂OH and-   R¹, R⁶, R⁷ are each as defined above    by reacting an alcohol of the formula V

with ammonia or a primary amine of the formula VI

R¹—NH₂  (VI).

The substituents R¹ to R¹², the variables X, Y, Z, and the indices j, k,l, m, n and q in the compounds I, II, III, IV, V, VI and VII are eachindependently defined as follows:

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²:

-   -   hydrogen (H),

R³, R⁴:

-   -   alkyl such as C₁₋₂₀-alkyl, preferably C₁₋₁₄-alkyl, such as        methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,        sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,        neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl,        cyclopentylmethyl, n-heptyl, isoheptyl, cyclohexylmethyl,        n-octyl, isooctyl 2-ethylhexyl, n-decyl, 2-n-propyl-n-heptyl,        n-tridecyl, 2-n-butyl-n-nonyl and 3-n-butyl-n-nonyl,    -   hydroxyalkyl such as C₁₋₂₀-hydroxyalkyl, preferably        C₁₋₈-hydroxyalkyl, more preferably C₁₋₄-hydroxyalkyl, such as        hydroxymethyl, 1-hydroxyethyl, 2-hydroxy-ethyl,        1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl and        1-(hydroxy-methyl)ethyl,    -   aminoalkyl such as C₁₋₂₀-aminoalkyl, preferably C₁₋₈-aminoalkyl,        such as aminomethyl, 2-aminoethyl, 2-amino-1,1-dimethylethyl,        2-amino-n-propyl, 3-amino-n-propyl, 4-amino-n-butyl,        5-amino-n-pentyl, N-(2-aminoethyl)-2-aminoethyl and        N-(2-aminoethyl)aminomethyl,    -   hydroxyalkylaminoalkyl such as C₂₋₂₀-hydroxyalkylaminoalkyl,        preferably C₃₋₈-hydroxyalkylaminoalkyl, such as        (2-hydroxyethylamino)methyl, 2-(2-hydroxyethyl-amino)ethyl and        3-(2-hydroxyethylamino)propyl,    -   R⁵—(OCR⁶R⁷CR⁸R⁹)_(n)—(OCR⁶R⁷), preferably        R⁵—(OCHR⁷CHR⁹)_(n)—(OCR⁶R⁷), more preferably        R⁵—(OCH₂CHR⁹)_(n)—(OCR⁶R⁷),    -   alkylaminoalkyl such as C₂₋₃₀-alkylaminoalkyl, preferably        C₂₋₂₀-alkylaminoalkyl, more preferably C₂₋₈-alkylaminoalkyl,        such as methylaminomethyl, 2-methyl-aminoethyl,        ethylaminomethyl, 2-ethylaminoethyl and 2-(isopropylamino)ethyl,        (R⁵)HN—(CH₂)_(q),    -   Y—(CH₂)_(m)—NR⁵—(CH₂)_(q),    -   heteroarylalkyl such as C₄₋₂₀-heteroarylalkyl, such as        pyrid-2-ylmethyl, furan-2-ylmethyl, pyrrol-3-ylmethyl and        imidazol-2-ylmethyl    -   alkylheteroaryl such as C₄₋₂₀-alkylheteroaryl, such as        2-methyl-3-pyridinyl, 4,5-di-methylimidazol-2-yl,        3-methyl-2-furanyl and 5-methyl-2-pyrazinyl,    -   heteroaryl such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,        pyrazinyl, pyrrol-3-yl, imidazol-2-yl, 2-furanyl and 3-furanyl,

R¹R², R³, R⁴:

-   -   cycloalkyl such as C₃₋₁₂-cycloalkyl, preferably C₃₋₈-cycloalkyl,        such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,        cycloheptyl and cyclooctyl, more preferably cyclopentyl and        cyclohexyl,    -   alkoxyalkyl such as C₂₋₃₀-alkoxyalkyl, preferably        C₂₋₂₀-alkoxyalkyl, more preferably C₂₋₈-alkoxyalkyl, such as        methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl,        n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl,        tert-butoxymethyl, 1-methoxyethyl and 2-methoxyethyl, more        preferably C₂₋₄-alkoxyalkyl,    -   dialkylaminoalkyl such as C₃₋₃₀-dialkylaminoalkyl, preferably        C₃₋₂₀-dialkylamino-alkyl, more preferably        C₃₋₁₀-dialkylaminoalkyl, such as N,N-dimethylaminomethyl,        (N,N-dibutylamino)methyl, 2-(N,N-dimethylamino)ethyl,        2-(N,N-diethyl-amino)ethyl, 2-(N,N-dibutylamino)ethyl,        2-(N,N-di-n-propylamino)ethyl and 2-(N,N-diisopropylamino)ethyl,        3-(N,N-dimethylamino)propyl, (R⁵)₂N—(CH₂)_(q),    -   aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl and 9-anthryl, preferably phenyl, 1-naphthyl and        2-naphthyl, more preferably phenyl,    -   alkylaryl such as C₇₋₂₀-alkylaryl, preferably C₇₋₁₂-alkylphenyl,        such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,        2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl,        3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl,        2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,        2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl,        4-ethylphenyl, 2-n-propylphenyl, 3-n-propylphenyl and        4-n-propylphenyl,    -   aralkyl such as C₇₋₂₀-aralkyl, preferably C₇₋₁₂-phenylalkyl,        such as benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl,        1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenylpropyl,        3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenyl-butyl and        4-phenylbutyl, more preferably benzyl, 1-phenethyl and        2-phenethyl,    -   R³ and R⁴ or R² and R⁴ together are a —(CH₂)_(l)—X—(CH₂)_(m)—        group such as —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—,        —(CH₂)—O—(CH₂)₂—, —(CH₂)—NR⁵—(CH₂)₂—, —(CH₂)—CHR⁵—(CH₂)₂—,        —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—NR⁵—(CH₂)₂—, —(CH₂)₂—CHR⁵—(CH₂)₂—,        —CH₂—O—(CH₂)₃—, —CH₂—NR⁵—(CH₂)₃—, —CH₂—CHR⁵—(CH₂)₃—,

R¹, R²:

-   -   alkyl such as C₁₋₂₀-alkyl, preferably C₁₋₈-alkyl, such as        methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,        sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,        neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl,        n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexyl, more        preferably C₁₋₄-alkyl, or    -   R¹ and R² together are a —(CH₂)_(j)—X—(CH₂)_(k) group such as        —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₇—,        —(CH₂)—O—(CH₂)₂—, —(CH₂)—NR⁵—(CH₂)₂—, —(CH₂)—CHR⁵—(CH₂)₂—,        —(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—NR⁵—(CH₂)₂—, —(CH₂)₂—CHR⁵—(CH₂)₂—,        —CH₂—O—(CH₂)₃—, —CH₂—NR⁵—(CH₂)₃—, —CH₂—CHR⁵—(CH₂)₃—,

R⁵, R¹⁰:

-   -   alkyl, preferably C₁₋₄-alkyl, such as methyl, ethyl, n-propyl,        isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,        preferably methyl and ethyl, more preferably methyl,    -   alkylphenyl, preferably C₇₋₄₀-alkylphenyl, such as        2-methylphenyl, 3-methyl-phenyl, 4-methylphenyl,        2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethyl-phenyl,        3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-, 3-, 4-nonylphenyl,        2-, 3-, 4-decylphenyl, 2,3-, 2,4-, 2,5-, 3,4-,        3,5-dinonylphenyl, 2,3-, 2,4-, 2,5-, 3,4- and 3,5-didecylphenyl,        in particular C₇₋₂₀-alkylphenyl,

R⁶, R⁷, R⁸, R⁹:

-   -   methyl or ethyl, preferably methyl,

R¹¹, R¹²:

-   -   alkyl such as C₁- to C₂₀-alkyl, cycloalkyl such as C₃- to        C₁₂-cycloalkyl, aryl, heteroaryl, aralkyl such as C₇- to        C₂₀-aralkyl, and alkylaryl such as C₇- to C₂₀-alkylaryl, in each        case as defined above,

X:

-   -   CH₂, CHR⁵, oxygen (O), sulfur (S) or NR⁵, preferably CH₂ and O,

Y:

-   -   N(R¹⁰)₂, preferably NH₂ and N(CH₃)₂,    -   hydroxyl (OH),    -   C₂₋₂₀-alkylaminoalkyl, preferably C₂₋₁₆-alkylaminoalkyl, such as        methylamino-methyl, 2-methylaminoethyl, ethylaminomethyl,        2-ethylaminoethyl and 2-(iso-propylamino)ethyl,    -   C₃₋₂₀-dialkylaminoalkyl, preferably C₃₋₁₆-dialkylaminoalkyl,        such as dimethylamino-methyl, 2-dimethylaminoethyl,        2-diethylaminoethyl, 2-(di-n-propylamino)ethyl and        2-(diisopropylamino)ethyl,

Z:

-   -   CH₂, CHR⁵, O, NR⁵ or NCH₂CH₂OH,        j, l:    -   an integer from 1 to 4 (1, 2, 3 or 4), preferably 2 and 3, more        preferably 2,        k, m, q:    -   an integer from 1 to 4 (1, 2, 3 or 4), preferably 2, 3 and 4,        more preferably 2 and 3,        n:    -   an integer from 1 to 30, preferably an integer from 1 to 8 (1,        2, 3, 4, 5, 6, 7 or 8), more preferably an integer from 1 to 6.

Suitable alcohols under the abovementioned prerequisites are virtuallyall primary and secondary alcohols with an aliphatic OH function. Thealcohols may be straight-chain, branched or cyclic. Secondary alcoholsare aminated just as efficiently as primary alcohols. The alcohols mayalso bear substituents or comprise functional groups which behaveinertly under the conditions of the hydrogenating amination, for examplealkoxy, alkenyloxy, alkylamino or dialkylamino groups, or else ifappropriate are hydrogenated under the conditions of the hydrogenatingamination, for example CC double or triple bonds. When polyhydricalcohols are to be aminated, it is possible via the control of thereaction conditions to obtain preferentially amino alcohols, cyclicamines or polyaminated products.

The amination of 1,4-diols leads, depending on the selection of thereaction conditions, to 1-amino-4-hydroxy compounds, 1,4-diaminocompounds, or to five-membered rings with a nitrogen atom(pyrrolidines).

The amination of 1,6-diols leads, depending on the selection of thereaction conditions, to 1-amino-6-hydroxy compounds, 1,6-diaminocompounds, or to seven-membered rings with a nitrogen atom(hexamethyleneimines).

The amination of 1,5-diols leads, depending on the selection of thereaction conditions, to 1-amino-5-hydroxy, 1,5-diamino compounds, or tosix-membered rings with a nitrogen atom (piperidines,1,5-dipiperidinylpentanes). It is accordingly possible to obtain fromdiglycol (DEG), by amination with NH₃, monoaminodiglycol(=ADG=H₂N—CH₂CH₂—O—CH₂CH₂—OH), diaminodiglycol (H₂N—CH₂CH₂—O—CH₂CH₂—NH₂)or more preferably morpholine. Piperazine is correspondingly obtainedwith particular preference from diethanolamine.N-(2-Hydroxyethyl)piperazine can be obtained from triethanolamine.

Preference is given to aminating, for example, the following alcohols:

methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,n-pentanol, n-hexanol, 2-ethylhexanol, tridecanol, stearyl alcohol,palmityl alcohol, cyclobutanol, cyclopentanol, cyclohexanol, benzylalcohol, 2-phenylethanol, 2-(p-methoxyphenyl)-ethanol,2-(3,4-dimethoxyphenyl)ethanol, 1-phenyl-3-butanol, ethanolamine,n-propanolamine, isopropanolamine, 2-amino-1-propanol,1-methoxy-2-propanol, 3-amino-2,2-dimethyl-1-propanol,n-pentanolamine(1-amino-5-pentanol), n-hexanol-amine(1-amino-6-hexanol), ethanolamine, diethanolamine, triethanolamine,N-alkyl-diethanolamines, diisopropanolamine,3-(2-hydroxyethylamino)propan-1-ol, 2-(N,N-dimethylamino)ethanol,2-(N,N-diethylamino)ethanol, 2-(N,N-di-n-propylamino)ethanol,2-(N,N-diisopropylamino)ethanol, 2-(N,N-di-n-butylamino)ethanol,2-(N,N-diisobutyl-amino)ethanol, 2-(N,N-di-sec-butylamino)ethanol,2-(N,N-di-tert-butylamino)ethanol, 3-(N,N-dimethylamino)propanol,3-(N,N-diethylamino)propanol, 3-(N,N-di-n-propylamino)propanol,3-(N,N-diisopropylamino)propanol, 3-(N,N-di-n-butylamino)propanol,3-(N,N-diisobutylamino)propanol, 3-(N,N-di-sec-butylamino)-propanol,3-(N,N-di-tert-butylamino)propanol, 1-dimethylaminopentanol-4,1-di-ethylaminopentanol-4, ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, diglycol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 2,2-bis[4-hydroxycyclohexyl]propane, methoxyethanol,propoxyethanol, butoxyethanol, polypropyl alcohols, polyethylene glycolethers, polypropylene glycol ethers and polybutylene glycol ethers. Thelatter polyalkylene glycol ethers are converted to the correspondingamines in the inventive reaction by converting their free hydroxylgroups.

Particularly preferred alcohols are methanol, ethanol, n-propanol,i-propanol, n-butanol, sec-butanol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 2-ethylhexanol, cyclohexanol, fatty alcohols, ethyleneglycol, diethylene glycol (DEG), triethylene glycol (TEG),2-(2-dimethylaminoethoxy)ethanol, N-methyldiethanolamine and2-(2-di-methylaminoethoxy)ethanol.

Suitable ketones usable in the process according to the invention are,under the abovementioned prerequisites, virtually all aliphatic andaromatic ketones. The aliphatic ketones may be straight-chain, branchedor cyclic; the ketones may comprise heteroatoms. The ketones may furtherbear substituents or comprise functional groups which behave inertlyunder the conditions of the hydrogenating amination, for example alkoxy,alkenyloxy, alkylamino or dialkylamino groups, or else, if appropriate,are hydrogenated under the conditions of the hydrogenating amination,for example C—C double or triple bonds. When polyfunctional ketones areto be aminated, it is possible via the control of the reactionconditions to obtain amino ketones, amino alcohols, cyclic amines orpolyaminated products.

Preference is given, for example, to aminatingly hydrogenating thefollowing ketones:

acetone, ethyl methyl ketone, methyl vinyl ketone, isobutyl methylketone, butanone, 3-methylbutan-2-one, diethyl ketone, tetralone,acetophenone, p-methylacetophenone, p-methoxyacetophenone,m-methoxyacetophenone, 1-acetylnaphthalene, 2-acetyl-naphthalene,1-phenyl-3-butanone, cyclobutanone, cyclopentanone, cyclopentenone,cyclohexanone, cyclohexenone, 2,6-dimethylcyclohexanone, cycloheptanone,cyclododecanone, acetylacetone, methylglyoxal and benzophenone.

Suitable aldehydes usable in the process according to the invention are,under the abovementioned prerequisites, virtually all aliphatic andaromatic aldehydes. The aliphatic aldehydes may be straight-chain,branched or cyclic; the aldehydes may comprise heteroatoms. Thealdehydes may further bear substituents or comprise functional groupswhich behave inertly under the conditions of the hydrogenatingamination, for example alkoxy, alkenyloxy, alkylamino or dialkylaminogroups, or else, if appropriate, are hydrogenated under the conditionsof the hydrogenating amination, for example C—C double or triple bonds.When polyfunctional aldehydes or keto aldehydes are to be aminated, itis possible via the control of the reaction conditions to obtain aminoalcohols, cyclic amines or polyaminated products.

Preference is given, for example, to aminatingly hydrogenating thefollowing aldehydes:

formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde,isobutyraldehyde, pivalaldehyde, n-pentanal, n-hexanal, 2-ethylhexanal,2-methylpentanal, 3-methyl-pentanal, 4-methylpentanal, glyoxal,benzaldehyde, p-methoxybenzaldehyde, p-methylbenzaldehyde,phenylacetaldehyde, (p-methoxyphenyl)acetaldehyde,(3,4-dimethoxyphenyl)acetaldehyde, 4-formyltetrahydropyran,3-formyltetrahydrofuran, 5-formylvaleronitrile, citronellal, lysmeral,acrolein, methacrolein, ethylacrolein, citral, crotonaldehyde,3-methoxypropionaldehyde, 3-aminopropionaldehyde, hydroxypivalaldehyde,dimethylolpropionaldehyde, dimethyloibutyraldehyde, furfural, glyoxal,glutaraldehyde and hydroformylated oligomers and polymers, for examplehydroformylated polyisobutene (polyisobutenealdehyde) or hydroformylatedoligomer obtained by metathesis of 1-pentene and cyclopentene.

The aminating agents used in the hydrogenating amination of alcohols,aldehydes or ketones in the presence of hydrogen may be either ammoniaor primary or secondary, aliphatic or cycloaliphatic or aromatic amines.

When the aminating agent used is ammonia, the alcoholic hydroxyl groupor the aldehyde group or the keto group is initially converted to theprimary amino groups (—NH₂). The primary amine thus formed may reactwith further alcohol or aldehyde or ketone to give the correspondingsecondary amine and this may in turn react with further alcohol oraldehyde or ketone to give the corresponding, preferably symmetrical,tertiary amine. Depending on the composition of the reaction mixture orof the reactant stream (in continuous mode), and depending on thereaction conditions employed—pressure, temperature, reaction time(catalyst hourly space velocity)—it is possible in this way to preparepreferentially primary, secondary or tertiary amines as desired.

In this way, it is possible to prepare, from polyhydric alcohols or di-or oligoaldehydes or di- or oligoketones or keto aldehydes, byintramolecular hydrogenating amination, cyclic amines, for examplepyrrolidines, piperidines, hexamethyleneimines, piperazines andmorpholines.

As well as ammonia, the aminating agents used may equally be primary orsecondary amines.

These aminating agents are preferably used to prepare unsymmetricallysubstituted di- or trialkylamines, such as ethyldiisopropylamine andethyldicyclohexylamine. For example the following mono- anddialkylamines are used as aminating agents: monomethylamine,dimethylamine, monoethylamine, diethylamine, n-propylamine,di-n-propylamine, isopropylamine, diisopropylamine, isopropylethylamine,n-butylamine, di-n-butylamine, s-butylamine, di-s-butylamine,isobutylamine, n-pentylamine, s-pentylamine, isopentylamine,n-hexylamine, s-hexylamine, iso-hexylamine, cyclohexylamine, aniline,toluidine, piperidine, morpholine and pyrrolidine.

Amines prepared with particular preference by the process according tothe invention are, for example, morpholine (from monoaminodiglycol),monoaminodiglycol, morpholine and/or 2,2′-dimorpholinodiethyl ether(DMDEE) (from DEG and ammonia), 6-dimethylaminohexanol-1 (fromhexanediol and dimethylamine (DMA)), triethylamine (from ethanol anddiethylamine (DEA)), dimethylethylamine (from ethanol and DMA),N—(C₁₋₄-alkyl)morpholine (from DEG and mono(C₁₋₄-alkyl)amine),N—(C₁₋₄-alkyl)piperidine (from 1,5-pentanediol andmono(C₁₋₄-alkyl)amine), piperazine and/or diethylenetriamine (DETA)(from N-(2-aminoethyl)ethanolamine (AEEA) and ammonia),N-methylpiperazine (from diethanolamine and MMA),N,N′-dimethylpiperazine (from N-methyldiethanolamine and MMA),1,2-ethylenediamine (EDA) and/or diethylenetriamine (DETA) and/or PIP(from monoethanolamine (MEOA) and ammonia), 2-ethylhexylamine andbis(2-ethylhexyl)amine (from 2-ethylhexanol and NH₃), tridecylamine andbis(tridecyl)amine (from tridecanol and NH₃), n-octylamine (fromn-octanol and NH₃), 1,2-propylenediamine (from 2-hydroxypropylamine andNH₃), 1-diethylamino-4-aminopentane (from1-diethylamino-4-hydroxypentane and NH₃),N,N-di(C₁₋₄-alkyl)cyclohexylamine (from cyclohexanone and/orcyclohexanol and di(C₁₋₄-alkyl)amine), e.g.N,N-dimethyl-N-cyclohexylamine (DMCHA), polyisobuteneamine (PIBA; where,for example, n˜1000) (from polyisobutenaldehyde and NH₃),N,N-diisopropyl-N-ethylamine (Hünig's base) (from N,N-diisopropylamineand acetaldehyde), N-methyl-N-isopropylamine (MMIPA) (frommonomethylamine and acetone), n-propylamines (such asmono-/di-n-propylamine, N,N-dimethyl-N-n-propylamine (DMPA)) (frompropionaldehyde and/or n-propanol and NH₃ or DMA),N,N-dimethyl-N-isopropylamine (DMIPA) (from i-propanol and/or acetoneand DMA), N,N-dimethyl-N-butylamines (1-, 2- or isobutanol and/orbutanal, i-butanal or butanone and DMA),2-(2-di(C₁₋₄-alkyl)aminoethoxy)ethanol and/orbis(2-di(C₁₋₄-alkyl)aminoethyl)ether (from DEG and di(C₁₋₄-alkyl)amine),1,2-ethylenediamine (EDA), monoethanolamine (MEOA), diethylenetriamine(DETA) and/or piperazine (PIP) (from monoethylene glycol (MEG) andammonia), 1,8-diamino-3,6-dioxaoctane and/or1-amino-8-hydroxy-3,6-dioxaoctane (from triethylene glycol (TEG) andammonia), 1-methoxy-2-propylamine (1-methoxyisopropylamine, MOIPA) (from1-methoxy-2-propanol and ammonia), N-cyclododecyl-2,6-dimethylmorpholine(dodemorph) (from cyclododecanone and/or cyclododecanol and2,6-dimethylmorpholine), polyetheramine (from corresponding polyetheralcohol and ammonia). The polyether alcohols are, for example,polyethylene glycols or polypropylene glycols having a molecular weightin the range from 200 to 5000 g/mol; the corresponding polyetheraminesare obtainable, for example, under the tradename PEA D230, D400, D2000,T403 or T5000 from BASF.

EXAMPLES Example 1 Preparation of Amination Catalyst 1 (Based onNi—Cu/ZrO₂=Comparative Experiment According to EP-A-697 39.5 andEP-A-696 572).

An aqueous solution of nickel nitrate, copper nitrate and zirconiumacetate which comprises 4.48% by weight of Ni (calculated as NiO), 1.52%by weight of Cu (calculated as CuO) and 2.82% by weight of Zr(calculated as ZrO₂) was precipitated simultaneously in a stirred vesselin a constant stream with a 20% aqueous sodium carbonate solution at atemperature of 70° C. in such a way that the pH, measured with a glasselectrode, of 7.0 was maintained. The resulting suspension was filteredand the filtercake was washed with demineralized water until theelectrical conductivity of the filtrate was approx. 20 μS. Sufficientammonium heptamolybdate was then incorporated into the still-moistfiltercake that the oxide mixture specified below was obtained.Thereafter, the filtercake was dried at a temperature of 150° C. in adrying cabinet or a spray dryer. The hydroxide-carbonate mixtureobtained in this way was then heat-treated at a temperature of from 450to 500° C. over a period of 4 hours. The catalyst thus prepared had thecomposition: 50% by weight of NiO, 17% by weight of CuO, 1.5% by weightof MoO₃ and 31.5% by weight of ZrO₂. The catalyst was mixed with 3% byweight of graphite and shaped to tablets. The oxidic tablets werereduced. The reduction was performed at 280° C. at a heating rate of 3°C./minute. Reduction was effected first with 10% H₂ in N₂ for 50minutes, then with 25% H₂ in N₂ for 20 minutes, then with 50% H₂ in N₂for 10 minutes, then with 75% H₂ in N₂ for 10 minutes and finally with100% H₂ for 3 hours. The percentages are each % by volume. Thepassivation of the reduced oxidic species was performed at roomtemperature in dilute air (air in N₂ with a maximum O₂ content of 5% byvolume).

Example 2

The catalyst was prepared analogously to catalyst 1, except that silvernitrate was additionally added to the nitrate solution. Furthermore,addition of ammonium heptamolybdate was dispensed with. The catalyst 2thus obtained has the composition as detailed in Table I.

Example 3 Amination of Diethylene Glycol (DEG)

8 g of the reduced amination catalyst in the form of approx. 1 mm spallwas initially charged in a 300 ml autoclave together with 80 g ofdiethylene glycol (0.75 mol). 34 g of liquid ammonia (2 mol) were addedto the reaction mixture, and the autoclave was injected with hydrogen to70 bar and heated to 200° C. At 200° C., hydrogen was again injected to20 bar, and the total pressure rose to 180-200 bar. The autoclave wasrun at 200° C. for 12 hours with stirring.

At different times, samples of the reaction mixture were taken andanalyzed by means of GC chromatography. For this purpose, a 30 m “RTX-5amine” GC column was used, with a temperature program of: 80° C./15minutes, heat to 290° C. within 30 minutes, at 290° C./15 minutes.

The composition of the resulting reaction mixtures for the catalysts ofExamples 1 to 2 can be taken from Table I.

TABLE I Doped catalysts based on Ni—Cu/ZrO2 Performance DEG Decarbo-Catalyst* Time Conversion Mor ADG MeOEt MeOAE nylation* Decarbonylation# Ni % Co % Cu % Dop. Dop. % Hours GC % GC % GC % GC % GC % Σ GC %normalized** % 1 41.4 — 15.2 Mo 1.5 4 59.3 18.8 29.05 0.21 0.07 0.350.58% 8 76.5 32.4 26.11 0.20 0.11 0.39 0.51% 12 93.2 50.7 14.21 0.160.17 0.49 0.53% 2 41.1 — 7.7 Ag 1.4 8 46.9 13.2 27.81 0.06 0.03 0.180.38% 10 71.0 28.2 30.47 0.07 0.05 0.19 0.27% 12 78.7 33.1 29.79 0.060.06 0.20 0.25% *Catalyst composition in % by weight; remainder up to100% is ZrO2 **Sum of decarbonylation/DEG conversion DEG diethyleneglycol Mor morpholine ADG aminodiglycol MeOEt methoxyethanol MeOAEmethoxyethylamine Decarbonylation Sum of methanol, methoxyethanol,methoxyethylamine N-methylmorpholine and methoxyethylmorpholine

Workup:

The particular pure products can be obtained from the aqueous crudematerials by rectification under reduced pressure, standard pressure orelevated pressure by the known methods. The pure products are obtainedeither directly in pure form or as azeotropes with water. Aqueousazeotropes can be dewatered by a liquid-liquid extraction withconcentrated sodium hydroxide solution before or after the purifyingdistillation. Distillative dewatering in the presence of an azeotropingagent by known methods is also possible.

In the case that the crude material or the aliphatic amine in the crudematerial is barely water-miscible, if at all, dewatering is alsopossible by a separation of the organic and of the aqueous phase byknown methods.

1-27. (canceled)
 28. A process comprising: (i) providing a reactantselected from the group consisting of primary alcohols, secondaryalcohols, aldehydes, ketones and mixtures thereof; and (ii) reacting thereactant with hydrogen and a nitrogen compound selected from the groupconsisting of ammonia, primary amines, secondary amines and mixturesthereof, in the presence of a catalyst comprising a zirconium dioxide-and nickel-containing catalytically active composition, to form anamine; wherein the catalytically active composition, prior to reductionwith hydrogen, comprises oxygen compounds of zirconium, copper, andnickel, and one or more oxygen compounds of silver in an amount of 0.5to 6% by weight, calculated as AgO.
 29. The process according to claim28, wherein, prior to reduction with hydrogen, the one or more oxygencompounds of silver is present in an amount of 1.0 to 4% by weight,calculated as AgO.
 30. The process according to claim 28, wherein, priorto reduction with hydrogen, the one or more oxygen compounds of silveris present in an amount of 1.3 to 3% by weight, calculated as AgO. 31.The process according to claim 28, wherein, prior to reduction withhydrogen, the catalytically active composition comprises: 10 to 75% byweight of an oxygen compound of zirconium, calculated as ZrO₂; 1 to 30%by weight of an oxygen compound of copper, calculated as CuO; and 10 to70% by weight of an oxygen compound of nickel, calculated as NiO. 32.The process according to claim 28, wherein, prior to reduction withhydrogen, the catalytically active composition comprises: 25 to 65% byweight of an oxygen compound of zirconium, calculated as ZrO₂; 2 to 25%by weight of an oxygen compound of copper, calculated as CuO; and 20 to60% by weight of an oxygen compound of nickel, calculated as NiO. 33.The process according to claim 28, wherein, prior to reduction withhydrogen, the catalytically active composition comprises: 30 to 55% byweight of an oxygen compound of zirconium, calculated as ZrO₂; 5 to 15%by weight of an oxygen compound of copper, calculated as CuO; and 30 to50% by weight of an oxygen compound of nickel, calculated as NiO. 34.The process according to claim 28, wherein nickel and copper are presentin the catalyst in a molar ratio of nickel to copper of greater than 1.35. The process according to claim 28, wherein the catalytically activecomposition contains no cobalt.
 36. The process according to claim 28,wherein the reaction is carried out at a temperature of 80 to 350° C.37. The process according to claim 28, wherein the reaction is carriedout in liquid phase and at an absolute pressure of 5 to 30 MPa.
 38. Theprocess according to claim 28, wherein the reaction is carried out ingas phase and at an absolute pressure of 0.1 to 40 MPa
 39. The processaccording to claim 28, wherein the reactant is reacted with 0.90 to 100times the molar amount of the nitrogen compound based on the amount ofthe reactant.
 40. The process according to claim 28, wherein thereactant is reacted with 1.0 to 10 times the molar amount of thenitrogen compound based on the amount of the reactant.
 41. The processaccording to claim 28, wherein the catalyst is present in a fixed bed.42. The process according to claim 28, wherein the reaction is carriedout continuously.
 43. The process according to claim 28, wherein thereaction is carried out in a tubular reactor.
 44. The process accordingto claim 42, wherein the reaction is carried out in a cycle gas method.45. The process according to claim 28, wherein one or both of thereactant and the nitrogen compound is present in the reaction as anaqueous solution.
 46. The process according to claim 28, wherein thereactant comprises diethylene glycol, wherein the nitrogen compoundcomprises ammonia, and wherein the amine comprises monoaminodiglycol andmorpholine.
 47. The process according to claim 28, wherein the reactantcomprises diethylene glycol, wherein the nitrogen compound comprises amono(C₁₋₄-alkyl)amine, and wherein the amine comprisesN—(C₁₋₄-alkyl)morpholine.
 48. The process according to claim 28, whereinthe reactant comprises diethylene glycol, wherein the nitrogen compoundcomprises a di(C₁₋₄-alkyl)amine, and wherein the amine comprises one orboth of 2-(2-di(C₁₋₄-alkyl)aminoethoxy)ethanol andbis(2-di(C₁₋₄-alkyl)aminoethyl)ether.
 49. The process according to claim28, wherein the reactant comprises monoethylene glycol, wherein thenitrogen compound comprises ammonia, and wherein the amine comprises oneor both of monoethanolamine and 1,2-ethylenediamine.
 50. The processaccording to claim 28, wherein the reactant comprises monoethanolamine,wherein the nitrogen compound comprises ammonia, and wherein the aminecomprises 1,2-ethylenediamine.
 51. The process according to claim 28,wherein the reactant comprises a polyether alcohol, wherein the nitrogencompound comprises ammonia, and wherein the amine comprises apolyetheramine corresponding to the polyether alcohol.
 52. The processaccording to claim 28, wherein the reactant comprisesN-(2-aminoethyl)ethanolamine, wherein the nitrogen compound comprisesammonia, and wherein the amine comprises one or both of piperazine anddiethylenetriamine.
 53. The process according to claim 28, wherein thereactant comprises polyisobutenaldehyde, wherein the nitrogen compoundcomprises ammonia, and wherein the amine comprises polyisobutenamine.54. A catalytically active composition comprising, prior to reductionwith hydrogen: 10 to 75% by weight of an oxygen compound of zirconium,calculated as ZrO₂; 1 to 30% by weight of an oxygen compound of copper,calculated as CuO; 10 to 70% by weight of an oxygen compound of nickel,calculated as NiO; and 0.5 to 6% by weight of an oxygen compound ofsilver, calculated as AgO.
 55. The catalytically active compositionaccording to claim 54, wherein the oxygen compound of silver is presentin an amount of 1.0 to 4% by weight, calculated as AgO.
 56. Thecatalytically active composition according to claim 54, wherein theoxygen compound of silver is present in an amount of 1.3 to 3% byweight, calculated as AgO.
 57. The catalytically active compositionaccording to claim 54, wherein the oxygen compound of zirconium ispresent in an amount of 25 to 65% by weight, calculated as ZrO₂; whereinthe oxygen compound of copper is present in an amount of 2 to 25% byweight, calculated as CuO; and wherein the oxygen compound of nickel ispresent in an amount of 20 to 60% by weight, calculated as NiO.
 58. Thecatalytically active composition according to claim 54, wherein theoxygen compound of zirconium is present in an amount of 30 to 55% byweight, calculated as ZrO₂; wherein the oxygen compound of copper ispresent in an amount of 5 to 15% by weight, calculated as CuO; andwherein the oxygen compound of nickel is present in an amount of 30 to50% by weight, calculated as NiO.
 59. The catalytically activecomposition according to claim 54, wherein nickel and copper are presentin a molar ratio of nickel to copper of greater than
 1. 60. Thecatalytically active composition according to claim 54, wherein thecomposition contains no cobalt.